CN104151473A - Modified styrene-maleic anhydride copolymer and thermosetting resin composition - Google Patents
Modified styrene-maleic anhydride copolymer and thermosetting resin composition Download PDFInfo
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Abstract
The invention provides a modified styrene-maleic anhydride copolymer which adopts the structural formula shown in the specification. The invention also provides a thermosetting resin composition including both the modified styrene-maleic anhydride copolymer and epoxy resin, and the composition is relatively low in dielectric constant and low in dielectric loss tangent and has excellent heat resistance, processing technology and storage performance. The invention further provides a prepreg and a laminate which are prepared from the thermosetting resin composition and both can be used as printed circuit substrate materials, PCBs and the like.
Description
Technical field
The invention belongs to technical field of electronic materials, be specifically related to a kind of upgrading type styrene-maleic anhydride copolymer and compositions of thermosetting resin thereof, and the prepreg and the veneer sheet that use this resin combination to make.
Background technology
In prior art, the material that epoxy resin and solidifying agent thereof prepared as compositions of thermosetting resin that must composition of take has good thermotolerance, insulativity, processibility and the advantage such as with low cost, therefore be widely used in, in the electronic materials such as semi-conductor, printed circuit board, having become starting material main in printed circuit board.
In recent years, along with the continuous propelling of information processing and information transmission high-speed high frequency technology, tellite material is being proposed to more and more higher requirement aspect dielectric properties.In simple terms, tellite material require possesses lower specific inductivity and dielectric loss tangent, delay, distortion and the loss of signal when reducing high-speed transfer, and the interference between signal.Therefore, expectation provides a kind of compositions of thermosetting resin, uses the printed circuit board material that this compositions of thermosetting resin is made can show fully low low-k and low-dielectric loss tangent at the signals transmission of high speed, high frequency.
Styrene-maleic anhydride copolymer has good reactivity worth, and the composition epoxy resin after it is curing has excellent dielectric properties, and therefore, its curing composition epoxy resin is often used to make the printed circuit board material in high-frequency high-speed field.When but anhydride type curing agent and epoxy resin are used in combination, there is a reactive problem: in the situation that not adding promotor, severe reaction conditions, requires temperature of reaction higher, but normal-temperature reaction is very fast under interpolation promotor, processing technology and storage property are all had a strong impact on.
In patent CN101845199A, mention, use the modification agent with hydroxyl to react with styrene-maleic anhydride copolymer, generate a kind of upgrading type styrene-maleic anhydride copolymer solidifying agent.But, this technology is to utilize hydroxyl or upgrading on hydroxyl modification agent to react rear newly-generated carboxyl as curing functional group cured epoxy resin, can in curing process, produce secondary hydroxyl like this, make the dielectric properties of cured article deteriorated, be that dielectricity constant and dielectric loss increase, be unfavorable for that it is in the application of high-frequency high-speed printed circuit board material.
Therefore, the present invention has researched and developed a kind of upgrading type styrene-maleic anhydride copolymer, thereby there is processing technology and storage property that suitable reactive behavior is improved the composition of itself and epoxy resin, there are excellent dielectric properties simultaneously, be suitable for the application in high-frequency high-speed printed circuit board material field.
Summary of the invention
The object of this invention is to provide a kind of upgrading type styrene-maleic anhydride copolymer and compositions of thermosetting resin thereof, and the prepreg and the veneer sheet that use this resin combination to make.
To achieve the above object of the invention, the present invention utilizes phenolic hydroxyl group compound or phenol sulfhydryl compound or hydroxylamine compound to react with styrene-maleic anhydride copolymer as modification agent, the anhydride group that plays solidification during using it as solidifying agent is transformed into active ester group, thereby obtains a kind of styrene-maleic anhydride copolymer solidifying agent of active ester modification.Described upgrading type styrene-maleic anhydride copolymer structural formula is as follows:
，
In formula, the integer that n is 1～30, the ratio that x, y are positive integer and x and y is 1:1～1:15, and preferred proportion is 1:1～1:10, and preferred ratio is 1:1～1:5;
R
1alkyl for hydrogen atom or C1～C5; R
2aliphatic alkyl for hydrogen atom, aromatic hydrocarbyl or C1～5; R
3, R
4independent separately, can be identical or different, be the alkyl of hydrogen atom, aromatic hydrocarbyl or C1～C8; R
5, R
6independent separately, can be identical or different, can be following group,
,
,
,
,
,
,
,
,
,
,
,
,
, R wherein
7for the aliphatic alkyl of hydrogen atom, nitro, halogen atom, cyano group, aromatic hydrocarbyl or C1～C5, preferred hydrogen atom, R
0for the alkyl of C1～C5, the phenylalkyl of the cycloalkyl of C1～C8, C7～C10, the alkylene of C3～C10, but R
5or R
6in have at most a group to be
.
In technique scheme, the R of described upgrading type styrene-maleic anhydride copolymer
5or R
6group, preferably maleimide phenoxyl, can obtain good resistance toheat, preferably
or
, can obtain good flame retardant properties.
In technique scheme, the number-average molecular weight of described upgrading type styrene-maleic anhydride copolymer is 1500～50000g/mol, and preferably 3000～30000 g/mol, are more preferably 5000～20000 g/mol.
In technique scheme, described upgrading type styrene-maleic anhydride copolymer can make by the following method: the multipolymer of use phenylethylene-maleic anhydride and phenolic hydroxyl group compound or phenol sulfhydryl compound or hydroxylamine compound carry out esterification and make under catalyst action.Also can make by the following method: first toxilic acid and phenolic hydroxyl group compound or phenol sulfhydryl compound or hydroxylamine compound are carried out to esterification under catalyst action and make maleic acid diester, then, maleic acid diester and vinylbenzene carry out Raolical polymerizable and make.Described catalyzer can be an acidic catalyst or basic catalyst, and an acidic catalyst can be phosphoric acid, sulfonic acid, Lewis acid etc., and basic catalyst can be sodium hydroxide, potassium hydroxide, DMAP, amine etc.
The present invention provides a kind of compositions of thermosetting resin simultaneously, comprising:
(1) epoxy resin;
(2) upgrading type styrene-maleic anhydride copolymer, its structure is as follows:
，
In formula, the integer that n is 1～30, the ratio that x, y are positive integer and x and y is 1:1～1:15, and preferred proportion is 1:1～1:10, and preferred ratio is 1:1～1:5;
R
1alkyl for hydrogen atom or C1～C5; R
2aliphatic alkyl for hydrogen atom, aromatic hydrocarbyl or C1～5; R3, R4 are independent separately, can be identical or different, be the alkyl of hydrogen atom, C1～C8, the aryl of the alkylaryl of C7-C15, C6-C10, the cycloalkyl of the aralkyl of C7-C15 or C3-C8; R
5, R
6independent separately, can be identical or different, can be following group,
,
,
,
,
,
,
,
,
,
,
,
,
, R wherein
7for the aliphatic alkyl of hydrogen atom, nitro, halogen atom, cyano group, aromatic hydrocarbyl or C1～C5, preferred hydrogen atom, R
0for the alkyl of C1～C5, the phenylalkyl of the cycloalkyl of C1～C8, C7～C10, the alkylene of C3～C10, but has at most a group to be in R5 or R6
; Wherein in the epoxy group(ing) of this epoxy resin and this upgrading type styrene-maleic anhydride copolymer, the molar ratio of ester group functional group is 1:5～4:1, and preferred proportion scope is 3:5～2:1.
In technique scheme, in described upgrading type styrene-maleic anhydride copolymer, to be the ratio of positive integer and x and y be 1:1～1:15 for x, y, and preferred proportion is 1:1～1:10, and preferred ratio is 1:1～1:5;
In technique scheme, the number-average molecular weight of described upgrading type styrene-maleic anhydride copolymer is 1500～50000g/mol, and preferably 3000～30000 g/mol, are more preferably 5000～20000 g/mol.
In technique scheme, described component (1) epoxy resin can be selected from bisphenol A epoxide resin, bisphenol F epoxy resin, phosphorous epoxy resin, nitrogen-containing epoxy thermoset, o-cresol formaldehyde epoxy resin, bisphenol-A phenolic epoxy resin, phenol novolac epoxy resins, cresol novolak epoxy, triphenyl methane epoxy resin, tetraphenyl ethane epoxy resin, biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, isocyanate-based epoxy resin, aralkyl novolac epoxy resin, alicyclic based epoxy resin, glycidyl amine type epoxy resin, in glycidyl ester type epoxy resin one or more.
Preferably, described component (1) epoxy resin is selected from one or more in biphenyl type epoxy resin, naphthalene nucleus type epoxy resin, dicyclopentadiene type epoxy resin, aralkyl novolac epoxy resin, phosphorous epoxy resin.
In technique scheme, compositions of thermosetting resin can also comprise that the solidifying agent such as amine compound, acid amides based compound, acid anhydrides based compound, phenol system compound, cyanate are as co-curing agent.Particularly, amine is that solidifying agent can be diaminodiphenyl-methane, diaminodiphenylsulfone(DDS), diethylenetriamine, bismaleimides, two carboxyl phthalic imidine, imidazoles etc.; Acid amides based compound can be Dyhard RU 100, Versamid etc.; Acid anhydrides based compound can be Tetra hydro Phthalic anhydride, trimellitic anhydride, pyromellitic acid anhydride, maleic anhydride, hydrogenation Tetra hydro Phthalic anhydride, carbic anhydride etc.; Phenol system compound can be phosphorus containing phenolic resin, Nitrogen-containing Phenolic Resins, bisphenol A phenolic resin, phenol resol, naphthol novolac resin, biphenyl modified phenolic resins, biphenyl modification naphthol resin, dicyclopentadiene phenol add-on type resin, phenol aralkyl resin, naphthols aralkyl resin, Pehanorm resin, benzoxazine colophony etc.
Preferably, the co-curing agent in the compositions of thermosetting resin of technique scheme is selected from one or more in following resin: bimaleimide resin, cyanate ester resin, naphthol novolac resin, biphenyl modified phenolic resins, biphenyl modification naphthol resin, dicyclopentadiene phenol add-on type resin, phosphorus containing phenolic resin.
Preferably, add cyanate ester resin as co-curing agent in the compositions of thermosetting resin of technique scheme, and the weight ratio of cyanate ester resin and component (1) epoxy resin is 100:20～100:300, preferred proportion is 100:50～100:200.Described cyanate ester resin can be selected from one or more in bisphenol A cyanate ester resin, Bisphenol F cyanate ester resin, bis-phenol M cyanate ester resin, dicyclopentadiene type ethylene rhodanate resin, o-cresol aldehyde type epoxy resin, phenol type cyanate ester resin.
Preferably, in the compositions of thermosetting resin of technique scheme, add bimaleimide resin as co-curing agent, and the weight ratio of bimaleimide resin and component (2) upgrading type vinylbenzene-maleoyl acid anhydride copolymer is 100:20～100:300, preferred proportion is 100:50～100:150, wherein the R in upgrading type vinylbenzene-maleoyl acid anhydride copolymer
5or R
6be preferably maleimide phenoxyl.Described bimaleimide resin is allyl group modified bismaleimide resin, and its number-average molecular weight is 2000～5000g/mol.
In technique scheme, described compositions of thermosetting resin can further include toughner, fire retardant, mineral filler and curing catalyst.
Described toughner can be high molecular phenoxy resin, rubber etc.
Described fire retardant can be bromide fire retardant, phosphorus flame retardant, nitrogenated flame retardant, organic silicon fibre retardant, organic metal salt fire retardant, inorganic flame retardant etc.Wherein, bromide fire retardant can be decabromodiphynly oxide, TDE, brominated styrene or tetrabromo-phthalic diformamide.Phosphorus flame retardant can be the general organophosphorus based compounds and 9 such as inorganic phosphorus, phosphate compound, phosphinic acid compounds, phosphinic compounds, phosphine oxide compound, organic system Nitrogen-and Phosphorus-containing compound, 10-dihydro-9 oxa--10-phosphine mix phenanthrene-10-oxide compound, 10-(2,5 dihydroxy phenyls)-9,10-dihydro-9 oxa--10-phosphine mix phenanthrene-10-oxide compound, 10-phenyl-9,10-dihydro-9-oxy is assorted-organophosphorus compound of the DOPO structures such as 10-phosphine phenanthrene-10-oxide compound and use it to react the derivative that forms etc. with the compound such as epoxy resin, resol.Nitrogenated flame retardant can be triaizine compounds, cyanuric acid compound, isocyanic acid compound, thiodiphenylamine etc.Organic silicon fibre retardant can be organic silicone oil, organo-silicone rubber, silicone resin etc.Organo-metallic fire retardant can be ferrocene, acetylacetone metal complex, organo-metallic carbonyl compound etc.Inorganic flame retardant can be aluminium hydroxide, magnesium hydroxide, aluminum oxide, barium oxide etc.
The content of described mineral filler amounts to 100 weight parts with respect to compositions of thermosetting resin, is 5～300 weight parts, is preferably 5～80 weight parts.Described mineral filler is selected from one or more in powdered quartz, fused silica, preparing spherical SiO 2, aluminum oxide, aluminium hydroxide, aluminium nitride, boron nitride, titanium dioxide, strontium titanate, barium titanate, barium sulfate, talcum powder, Calucium Silicate powder, calcium carbonate, mica, tetrafluoroethylene.
Described curing catalyst adds and uses according to practical situation, can be selected from dimethyl aminopyridine, tertiary amine and salt thereof, imidazoles, organic metal salt, triphenylphosphine Ji Qi phosphonium salt etc.
In technique scheme, in described compositions of thermosetting resin, can also add additives such as using silane coupling agent, pigment, emulsifying agent, dispersion agent according to actual feelings.
Above-mentioned compositions of thermosetting resin, can be for the manufacture of semiconductor-encapsulating material, adhering film, binding agent, resin cast material, conductive paste etc. for lamination.
The present invention asks for protection the prepreg that adopts above-mentioned resin combination to make simultaneously, and above-mentioned resin combination is made to glue by dissolution with solvents, then strongthener is immersed in above-mentioned glue; After flooding, after strongthener heat drying, can obtain described prepreg.
Described solvent is selected from one or more in acetone, butanone, toluene, mibk, N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, ethylene glycol monomethyl ether, propylene glycol monomethyl ether.Described strongthener can adopt natural fiber, organic synthetic fibers, organic fabric or without woven fabrics.
Strongthener is immersed in glue, heat drying then, heat drying 1-30 minute at the temperature of 100-200 degree, makes it semicure conventionally.
The present invention asks for protection the veneer sheet that adopts above-mentioned resin combination to make simultaneously; at a single or double by above-mentioned prepreg, be covered with tinsel; or after at least 2 are superposeed by above-mentioned prepreg; at its single or double, be covered with tinsel; hot compacting, can obtain described veneer sheet.
The quantity of described prepreg is that veneer sheet thickness is as requested determined, available one or more.Described tinsel, so long as the material using in electrically insulating material purposes all can, be not particularly limited, can be Copper Foil, can be also aluminium foil, and their thickness be not particularly limited.In addition, molding condition is veneer sheet and multiple-plate method for applicable electrically insulating material for example, such as using multiple deck press, multi-layer vacuum press, continuous molding, hot compacting machine etc., at temperature 100-250 ℃, pressure 2-100kg/cm2, the scope internal shaping of 0.1-5 hour heat-up time.
Beneficial effect of the present invention: resin combination of the present invention not only has good dielectric properties, and there is excellent complete processing controllability, in the situation that adding promotion, have suitable reactive behavior, compared with prior art, the operability in the course of processing significantly improves.The veneer sheet being made by compositions of thermosetting resin of the present invention has excellent dielectric properties, compared with prior art, specific inductivity and dielectric loss all decline to a great extent, and at the signals transmission of high speed, high frequency, can show fully low low-k and low-dielectric loss tangent.
Embodiment
To further describe by specific embodiment below.Yet should be appreciated that specific embodiment is only for explaining the present invention, the protection domain being not intended to limit the present invention.In the application, instrument used, equipment, reagent, method etc., as do not specialized, are the conventional instrument in this area, equipment, reagent and method.In situation without special instruction, " part " representative " weight part ", " % " representative " % by weight ".
Embodiment 1～4th, upgrading type styrene-maleic anhydride copolymer of the present invention synthetic, comparative example 1 is the synthetic of phenolic hydroxyl group group upgrading type styrene-maleic anhydride copolymer, embodiment 5～10 and comparative example 2～3rd, the preparation of compositions of thermosetting resin and performance evaluation.
Embodiment 1
By ethyl acetate, by the ratio of styrene-maleic anhydride copolymer resin 250g(vinylbenzene and maleic anhydride, be 4:1), dicyclohexylcarbodiimide 110g, phenol 100g fully dissolves to be placed in three neck reaction flasks and fully mixes, then under agitation add 1.0g4-Dimethylamino pyridine, under room temperature, react 8 hours, reaction soln being placed in to cooling for some time under the low temperature environment of 0～5 ℃ then filters to isolate solid impurity, then by the product distillation making, purifying makes the styrene-maleic anhydride copolymer A-1 that phenol is modified, it is 8000g/mol that GPC method records its number-average molecular weight, structural formula is as follows:
In formula, the integer that n is 1～30, the ratio that x, y are positive integer and x and y is 4:1; R1, R2, R3, R4 are hydrogen atom, and R5, R6 are phenoxy group.
Embodiment 2
By ethyl acetate by styrene-maleic anhydride copolymer resin 150g (ratio of vinylbenzene and maleic anhydride is 2:1), dicyclohexylcarbodiimide 110g, 3-hydroxyl-1, 2, 3-phentriazine-4 (3H)-one 170g fully dissolves to be placed in three neck reaction flasks and fully mixes, then under agitation add 3.0g4-Dimethylamino pyridine, under room temperature, react 10 hours, reaction soln being placed in to cooling for some time under the low temperature environment of 0～5 ℃ then filters to isolate solid impurity, then by the product distillation making, purifying makes 3-hydroxyl-1, 2, the styrene-maleic anhydride copolymer A-2 that 3-phentriazine-4 (3H)-one is modified, use GPC method to record its number-average molecular weight for 13000g/mol, structural formula is as follows:
In formula, the integer that n is 1～30, the ratio that x, y are positive integer and x and y is 2:1; R1, R2, R3, R4 are hydrogen atom, and R5, R6 are
.
Embodiment 3
With tetrahydrofuran (THF) by styrene-maleic anhydride copolymer resin 100g (ratio of vinylbenzene and maleic anhydride is 1:1), dicyclohexylcarbodiimide 110g, N-(4-hydroxy phenyl) maleimide 200g fully dissolves to be placed in three neck reaction flasks and fully mixes, then under agitation add 2.0g4-Dimethylamino pyridine, under room temperature, react 10 hours, reaction soln being placed in to cooling for some time under the low temperature environment of 0～5 ℃ then filters to isolate solid impurity, then by the product distillation making, purifying makes the amine-modified styrene-maleic anhydride copolymer A-3 of N-(4-hydroxy phenyl) maleimide, use GPC method to obtain its number-average molecular weight for 21000g/mol, structural formula is as follows:
In formula, the integer that n is 1～30, the ratio that x, y are positive integer and x and y is 1:1; R1, R2, R3, R4 are hydrogen atom, and R5, R6 are 4-maleimide phenoxyl.
Embodiment 4
By ethyl acetate, styrene-maleic anhydride copolymer resin 350g (vinylbenzene is 6:1 with the ratio of maleic anhydride), phenol 50g are fully dissolved to be placed in three neck reaction flasks and fully mixed, then under agitation add 0.5g4-Dimethylamino pyridine, under room temperature, react 5 hours.Then, in anti-reaction flask, add dicyclohexylcarbodiimide, 16g methyl alcohol and the 0.5g4-Dimethylamino pyridine that 110g has dissolved, after fully stirring, under normal temperature, react 5 hours.Then, reaction soln being placed in to cooling for some time under the low temperature environment of 0～5 ℃ then filters to isolate solid impurity, then the product distillation, the purifying that make are made to the styrene-maleic anhydride copolymer A-4 that phenol and methyl alcohol are modified, use GPC method to record its number-average molecular weight for 6000g/mol, structural formula is as follows:
In formula, the integer that n is 1～30, the ratio that x, y are positive integer and x and y is 6:1; R1, R2, R3, R4 are hydrogen atom, and R5 phenoxy group, R6 are methoxyl group.
Comparative example 1
With toluene, by the ratio of styrene-maleic anhydride copolymer resin 250g(vinylbenzene and maleic anhydride, be 4:1) be placed in three neck reaction flasks and see with the third diphenol 120g, under room temperature, be dissolved in toluene completely, the second two base aniline that add 0.5g under stirring, then be warming up to 70～80 ℃ of reactions 4 hours, obtain styrene-maleic anhydride copolymer resin B-1 that the third diphenol is modified, its structural formula is as follows:
In formula, the integer that n is 1～30, the ratio that x, y are positive integer and x and y is 4:1; R group is
。
Embodiment 5～10 and comparative example 2～3
The formula of recording according to table 1, it is 60% resin adhesive liquid that all components is mixed with to solid content, curing catalyst adds according to the amount of 0.5phr.
Then on gelation time tester, test the gelation time of glue in order to the reactivity of evaluating resin composition, thereby evaluating resin is combined in processing performance in the course of processing, test condition is 171 ℃.
Then make under the following conditions veneer sheet, and by following method evaluation flame retardant resistance, wet-hot aging performance and dielectric characteristics.The results are shown in table 1.
< veneer sheet manufacturing conditions >
Base material: ordinary electronic level 2116 glass-fiber-fabrics;
The number of plies: 5;
Sheet metal thickness after moulding: 1.0mm;
Preimpregnation semicure condition: 165 ℃/5min;
Condition of cure: 150 ℃/60min+190 ℃/120min;
< thermotolerance is second-order transition temperature (Tg) sign thermotolerance for >, according to dsc, according to the DSC method of IPC-TM-650 2.4.25 defined, measures.
The mensuration > specific inductivity of < specific inductivity and dielectric loss tangent is used flat band method according to IPC-TM-650 2.5.5.9, measures the specific inductivity under 1GHz; Dielectric loss tangent: use flat band method according to IPC-TM-650 2.5.5.9, measure the dielectric loss factor under 1GHz.
< flame retardant resistance > measures according to UL94 method.Not fire-retardant use " No " represents.
Table 1 explanation:
The upgrading type styrene-maleic anhydride copolymer (A-1) making in A-1: embodiment 1;
The upgrading type styrene-maleic anhydride copolymer (A-2) making in A-2: embodiment 2;
The upgrading type styrene-maleic anhydride copolymer (A-3) making in A-3: embodiment 3;
The upgrading type styrene-maleic anhydride copolymer (A-4) making in A-4: embodiment 3;
B-1: the upgrading type styrene-maleic anhydride copolymer (B-1) making in comparative example 1;
SMA: self-control styrene-maleic anhydride copolymer, the mol ratio of vinylbenzene and maleic anhydride is 3:1;
Epoxy resin 1: dicyclopentadiene type resol, chemical drug, epoxy equivalent (weight) 265g/eq;
Epoxy resin 2: phosphorous epoxy resin, CHIN YEE PE-315, epoxy equivalent (weight) 240g/eq, phosphorus content 3.5%wt;
Equivalence ratio: the equivalence ratio of active ester groups in epoxy group(ing) and upgrading type Zelan 338;
Cyanate: bisphenol A cyanate ester resin, Lonza, BA-3000S;
Bismaleimides: self-control allyl group modified BMI resin prepolymer, synthetic method is by 100 parts of bimaleimide resins and 50 parts of allylic cpds, at 130 degree temperature, react 85min, reaction is cooled to room temperature after finishing and obtains, and its number-average molecular weight is 3500g/mol;
Phosphorus-containing phenolic aldehyde: Dow 92741 phosphorus content 9.2%wt;
Toughner: nucleocapsid particles toughner, EVONIK;
Curing catalyst: 2-methyl-4-ethyl imidazol(e);
Filler: silicon-dioxide.
From upper table 1, what embodiment 5～10 adopted is the upgrading type styrene-maleic anhydride copolymer cured epoxy resin in the present invention, compare the comparative example 2 of using phenolic hydroxyl group upgrading type styrene-maleic anhydride copolymer cured epoxy resin, obviously reduced the low-k after epoxy resin cure, low-dielectric loss tangent.Embodiment 5～10 and comparative example 3 relatively, have suitable gelation time, show that resin system has suitable reactivity, is conducive to the improvement of processing technology.Embodiment 8 has added the resin system of cyanate ester resin as co-curing agent, compares embodiment 5～7, has more excellent resistance toheat and dielectric properties.Embodiment 9 has added the resin system of bimaleimide resin as co-curing agent, compares embodiment 5～7, has more excellent resistance toheat and dielectric properties.
Claims (10)
1. a upgrading type styrene-maleic anhydride copolymer, is characterized in that, the structural formula of described upgrading type styrene-maleic anhydride copolymer is as follows:
，
In formula, the integer that n is 1～30, x, y are positive integer; R
1alkyl for hydrogen atom or C1～C5; R
2aliphatic alkyl for hydrogen atom, aromatic hydrocarbyl or C1～C5; R
3, R
4independent separately, can be identical or different, be the alkyl of hydrogen atom, aromatic hydrocarbyl or C1～C8; R
5, R
6independent separately, can be identical or different, be selected from following group:
,
,
,
,
,
,
,
,
,
,
,
,
, R wherein
7for the aliphatic alkyl of hydrogen atom, nitro, halogen atom, cyano group, aromatic hydrocarbyl or C1～C5, R
0for the alkyl of C1～C5, the phenylalkyl of the cycloalkyl of C1～C8, C7～C10, the alkylene of C3～C10, but R
5or R
6in have at the most a group to be
, the number-average molecular weight of described upgrading type styrene-maleic anhydride copolymer is 1500～50000g/mol.
2. upgrading type styrene-maleic anhydride copolymer according to claim 1, is characterized in that, the ratio of described x and y is 1:1～15:1.
3. upgrading type styrene-maleic anhydride copolymer according to claim 1, is characterized in that described R
5or R
6group be selected from maleimide phenoxyl,
or
.
4. a compositions of thermosetting resin, comprising:
(1) epoxy resin;
(2) the upgrading type styrene-maleic anhydride copolymer described in claim 1-3 any one,
Wherein in the epoxy group(ing) of this epoxy resin and this upgrading type styrene-maleic anhydride copolymer, the molar ratio of ester group functional group is 1:5～4:1.
5. compositions of thermosetting resin according to claim 4, it is characterized in that, described compositions of thermosetting resin also comprises co-curing agent, described solidifying agent is selected from amine compound, acid amides based compound, acid anhydrides based compound, phenol system compound, cyanate ester resin, preferably in bimaleimide resin, cyanate ester resin, naphthol novolac resin, biphenyl modified phenolic resins, biphenyl modification naphthol resin, dicyclopentadiene phenol add-on type resin, phosphorus containing phenolic resin at least one.
6. compositions of thermosetting resin according to claim 5, is characterized in that, described co-curing agent is cyanate ester resin, and the weight ratio of cyanate ester resin and epoxy resin is 100:20～100:300.
7. resin combination according to claim 5, is characterized in that: described co-curing agent is bimaleimide resin, and the weight ratio of bismaleimides and upgrading type vinylbenzene-maleoyl acid anhydride copolymer is 100:20～100:300.
8. according to the compositions of thermosetting resin described in claim 4～7 any one, it is characterized in that, also comprise toughner, mineral filler, fire retardant and curing catalyst.
9. a prepreg, is characterized in that, the compositions of thermosetting resin described in claim 4～8 any one is made to glue by dissolution with solvents, then strongthener is immersed in above-mentioned glue; By after the strongthener heat drying after dipping, can obtain described prepreg.
10. a veneer sheet, is characterized in that, at the single or double of a prepreg claimed in claim 9, is covered with tinsel, or by after at least 2 prepregs stacks claimed in claim 9, at its single or double, be covered with tinsel, hot compacting, can obtain described veneer sheet.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336662A (en) * | 2016-08-29 | 2017-01-18 | 苏州生益科技有限公司 | Thermosetting resin composition and prepreg and laminated board manufactured from same |
| CN107365400A (en) * | 2017-07-12 | 2017-11-21 | 中国科学院新疆理化技术研究所 | A kind of synthetic method of styrene dicyclopentadiene monomaleate copolymer |
| CN108727775A (en) * | 2017-04-21 | 2018-11-02 | 南亚塑胶工业股份有限公司 | It is resistance to combustion modification type styrene maleic resin curing agent preparation method and epoxy resin composition and its in copper clad laminate and film application |
| CN109096262A (en) * | 2017-06-20 | 2018-12-28 | 台光电子材料股份有限公司 | Vinyl modified maleimides, compositions and articles thereof |
| US10815372B2 (en) | 2017-03-27 | 2020-10-27 | Nan Ya Plastics Corporation | Process for the preparation of a flame-retardant modified styrene-maleic anhydride resin and a composition of epoxy resins and their application to copper clad laminate and prepreg |
| TWI765504B (en) * | 2020-12-30 | 2022-05-21 | 聯茂電子股份有限公司 | LOW EXPANSION COEFFICIENT, LOW Df, HIGH RIGIDITY, HALOGEN-FREE RESIN COMPOSITION, LAMINATES AND PRINTED CIRCUIT BOARDS |
| CN115948101A (en) * | 2023-01-06 | 2023-04-11 | 深圳市金川防水防腐装饰工程有限公司 | Water-resistant anticorrosive epoxy resin coating and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106336662A (en) * | 2016-08-29 | 2017-01-18 | 苏州生益科技有限公司 | Thermosetting resin composition and prepreg and laminated board manufactured from same |
| US10815372B2 (en) | 2017-03-27 | 2020-10-27 | Nan Ya Plastics Corporation | Process for the preparation of a flame-retardant modified styrene-maleic anhydride resin and a composition of epoxy resins and their application to copper clad laminate and prepreg |
| CN108727775A (en) * | 2017-04-21 | 2018-11-02 | 南亚塑胶工业股份有限公司 | It is resistance to combustion modification type styrene maleic resin curing agent preparation method and epoxy resin composition and its in copper clad laminate and film application |
| CN108727775B (en) * | 2017-04-21 | 2020-12-25 | 南亚塑胶工业股份有限公司 | Preparation method of flame-retardant modified styrene maleic anhydride resin hardener, epoxy resin composition and application of epoxy resin composition in copper foil substrate and film |
| CN109096262A (en) * | 2017-06-20 | 2018-12-28 | 台光电子材料股份有限公司 | Vinyl modified maleimides, compositions and articles thereof |
| CN109096262B (en) * | 2017-06-20 | 2021-06-15 | 台光电子材料股份有限公司 | Vinyl modified maleimides, compositions and articles thereof |
| CN107365400A (en) * | 2017-07-12 | 2017-11-21 | 中国科学院新疆理化技术研究所 | A kind of synthetic method of styrene dicyclopentadiene monomaleate copolymer |
| TWI765504B (en) * | 2020-12-30 | 2022-05-21 | 聯茂電子股份有限公司 | LOW EXPANSION COEFFICIENT, LOW Df, HIGH RIGIDITY, HALOGEN-FREE RESIN COMPOSITION, LAMINATES AND PRINTED CIRCUIT BOARDS |
| CN115948101A (en) * | 2023-01-06 | 2023-04-11 | 深圳市金川防水防腐装饰工程有限公司 | Water-resistant anticorrosive epoxy resin coating and preparation method thereof |
| CN115948101B (en) * | 2023-01-06 | 2023-09-26 | 深圳市金川防水防腐装饰工程有限公司 | Waterproof and anticorrosive epoxy resin coating and preparation method thereof |
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